Sulfur-containing organic-inorganic hybrid gel compositions and aerogels

ABSTRACT

Methods and materials are described for preparing organic-inorganic hybrid gel compositions where a sulfur-containing cross-linking agent covalently links the organic and inorganic components. The gel compositions are further dried to provide porous gel compositions and aerogels. The mechanical and thermal properties of the dried gel compositions are also disclosed.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.14/818,943, filed Aug. 5, 2015; which is a divisional application ofU.S. patent application Ser. No. 13/399,871, filed Feb. 17, 2012; whichclaims the benefit of U.S. Provisional Application 61/503,389, filedJun. 30, 2011; which applications are hereby incorporated by referencein their entirety as if fully set forth, insofar as the incorporatedsubject matter does not conflict with the subject matter of the currentapplication.

GOVERNMENT INTEREST

This invention was made with the United States Government support underContract no. NNX08CB59P awarded by NASA. The Government has certainrights in the invention.

DESCRIPTION

Aerogels describe a class of material based upon their structure, namelylow density, open cell structures, large surface areas (often 900 m²/gor higher) and sub-nanometer scale pore sizes. Supercritical andsubcritical fluid extraction technologies are commonly used to extractthe fluid from the fragile cells of the material. A variety of differentaerogel compositions are known and they may be inorganic, organic andinorganic/organic hybrid (see N. Hüising and U Schubert, Angew. Chem.Int. Ed. 1998, 37, 22-45). Inorganic aerogels are generally based uponmetal alkoxides and include materials such as silica, carbides, andalumina. Organic aerogels include, but are not limited to, urethaneaerogels, resorcinol formaldehyde aerogels, and polyimide aerogels.Organic/inorganic hybrid aerogels were mainly organically modifiedsilicate materials. The organic components are covalently bonded to thesilica network. In other words, the organic and inorganic phases arechemically bonded to each other in the inorganic/organic hybridaerogels. The present invention involves such covalently bondedinorganic/organic hybrid aerogels.

Aerogel materials of the present invention with densities 0.01-0.5 g/ccare the best solid thermal insulators, better than the best rigid foamswith thermal conductivities of 10 mW/m-K and below at 100° F. andatmospheric pressure. Aerogels of the present invention function asthermal insulators primarily by minimizing conduction (low density,tortuous path for heat transfer through the solid nanostructure),convection (very small pore sizes minimize convection), and radiation(IR absorbing or scattering dopants are readily dispersed throughout theaerogel matrix). Depending on the formulation, they can function well atcryogenic temperatures to 550° C. and above. Aerogel materials of thepresent invention also display many other interesting acoustic, optical,mechanical, and chemical properties that make them abundantly useful.The methods described in this invention represent advances in gelformations that will facilitate production and improved properties ofthese aerogel materials.

Aerogels of the present invention are formed from flexible gelprecursors. Various flexible layers, including flexible fiber-reinforcedaerogels, are readily combined and shaped to give pre-forms that whenmechanically compressed along one or more axes, give compressivelystrong bodies along any of those axes. Aerogel bodies that arecompressed in this manner exhibit much better thermal insulation valuesthan incumbent insulation materials.

Methods for gel monolith and/or fiber-reinforced composite gelproduction formed via sol-gel chemistry involve batch casting. Batchcasting is defined herein as catalyzing one entire volume of sol toinduce gelation simultaneously throughout that volume. Gel-formingtechniques are well-known to those trained in the art: examples includeadjusting the pH and/or temperature of a dilute metal oxide sol to apoint where gelation occurs (R. K. Iler, Colloid Chemistry of Silica andSilicates, 1954, chapter 6; R. K. Iler, The Chemistry of Silica, 1979,chapter 5, C. J. Brinker and G. W. Scherer, Sol-Gel Science, 1990,chapters 2 and 3). Suitable materials for forming inorganic aerogels areoxides of most of the metals that can form oxides, such as silicon,aluminum, titanium, zirconium, hafnium, yttrium, vanadium, and the like.Particularly preferred are gels formed primarily from alcohol solutionsof hydrolyzed silicate esters due to their ready availability and lowcost (alcogel).

The sol-gel process is used to synthesize a large variety of inorganicand hybrid inorganic-organic xerogels, aerogels and nanocompositematerials. Relevant precursor materials for silica based aerogelsynthesis include, but are not limited to, sodium silicates,tetraethylorthosilicate (TEOS), tetramethylorthosilicate (TMOS),monomeric alkylalkoxy silanes, bis trialkoxy alkyl or aryl silanes,polyhedral silsesquioxanes, and others. Various polymers have beenincorporated into silica gels to improve mechanical properties of theresulting gels, xerogels (see J. D. Mackenzie, Y. J. Chung and Y. Hu, J.Non-Crystalline solid 147&148 (1992), 271-279; and Y. Hu and J. D.Mackenzie. J. Mater. Science, 27, (1992)), and aerogels (see S. J.Kramer, F. Rubio-Alonso and J. D. Mackenzie, MRS Proc. Vol 435, 295-300,1996). Aerogels are typically obtained when the gels are dried in amanner that does not alter or causes minimal changes to the structure ofthe wet gel. This is typically accomplished by removing the solventphase from the gel above the critical point of the solvent or mixture ofsolvents if a co-solvent is used to aid the drying process. However, thesurface of the wet-gels of the present invention may be treated withsilylating agents such as Hexamethylsilazane or other chemicals suchthat they are made strong enough to withstand any collapsing forcesduring drying conducted below the critical point and even at ambientpressures and at ambient or elevated temperatures.

Covalently bonded hybrid aerogel materials are produced by using variouscross linking agents as bridges between the inorganic and organiccomponents. However, the choice of the cross linking agent influencesthe properties of the resulting materials considerably. The presentinvention employs sulfur based cross linking agents and in particular,sulfidosilanes and/or tetra and hexasulfides, to bridge theorganic-inorganic components. Polybutadiene as the unsaturated organicpolymer and bis(triethoxysilylpropyl)tetrasulfide (TESPT) as the sulfurcontaining cross linking agent are used as examples to illustrate thecapabilities of the present invention. However, many other similarmaterials described here and elsewhere may be substituted for theunsaturated organic polymer and the sulfur containing cross linkingagent to practice the present invention.

Illustrative examples of unsaturated organic polymers useful in thepresent invention include, but not limited to, unsaturated polyesters,prepolymers based on vinylesters, acrylates, methacrylates orpolyurethanes, polybutadiene, polystyrene, polyisoprene, co-polymerssuch as styrene-butadiene copolymer, butadiene-isoprene co-polymer,buradiene,-isoprene-styrene ter polymer, copolymer-terpolymer ofisobutylene, para-methylstyrene and bromo-para-methylstyrene, EPDMrubber, or any combination of the foregoing.

Illustrative examples of sulfur-containing cross linking agents usefulin the present invention include, but not limited to, polysulfide alkylsilanes, mercapto aryl silanes, polysulfide aryl silanes such as thosedescribed in German Pat. Nos. 1, 000,817 and 2,141,159 and U.S. Pat. No.2,719,165 and U.S. Pat. No. 4,044,037, silated core polysulfidesdescribed in U.S. Pat. No. 7,696,269 and U.S. Pat. No. 7,687,558,silated cyclic core polysulfides, including those described in U.S. Pat.No. 7,968,634, U.S. Pat. No. 7,968,636, sulfur-containing silanesdescribed in U.S. Pat. No. 7,786,200 and U.S. Pat. No. 6,518,335,Sulfanylsilanes described in U.S. Pat. No. 6,229,036, sulfur-containingsiloxanes, Sulfur-functional polyorganosiloxanes such as those describedin U.S. Pat. No. 6,472,481, bis(triethoxysilylpropyl)tetrasulfide(TESPT), 3-thiocyanatopropyltriethoxysilane,3-mercaptopropyltrimethoxysilane or any combination of the foregoing.

Additionally, fiber reinforcements may be added to the gels to produce awet gel sheet that may be subsequently dried to produce aerogelcomposites. Fiber reinforcements may be in the form of discrete fibersor non-woven structures like battings, matts, felts of one or moreorganic or inorganic fibrous materials. When non-woven structures areused, it is preferable to use them in a continuous sheet to produce acontinuous gel sheet of fiber reinforced hybrid gels of the presentinvention. Such sheets may be rolled and dried, preferably such thatthey substantially retain an open pore structure.

The loading of each component such as the organic polymer, cross-linkingagents, inorganic materials such as silica may be varied to change theproperties of the resulting composites. When fiber reinforcement ispreferred, the amount of fiber is also available as a variable tocontrol various properties, including mechanical strength, flexibility,thermal conductivity, opacity, transparence, etc. Organic polymer may beadded up to 80 wt % and preferably up to 50 wt % and more preferably upto 30 wt % of the overall weight of the gel composition. The crosslinking agents may be added up to 30 wt %, preferably up to 15 wt % andmore preferably up to 5 wt % of the gel composition.

The gel compositions of the present invention may be prepared by threemajor steps. First would be to prepare a silane-functionalized organicpolymer. This step may be performed in aqueous medium or in anon-aqueous medium. The second step would be to react the functionalizedorganic polymer with an inorganic gel precursor, typically a silicaprecursor, but it may be of any metal oxide type. In the case of silica,it may be a hydrolyzed alkoxy silane or a sol prepared from water glass(sodium silicate). As such, the functionalized organic polymer isreacted with the inorganic sol and allowed to gel. This sol-gel processmay be controlled using all the variables typically available in asol-gel process as understood in the art. Before it is gelled,additional ingredients like opacifiers or reinforcement fibers may beadded. Third major step would be to dry the gel to prepare a porousbody. Drying may be accomplished through a ambient pressure drying or ahigh-pressure or alternatively a drying involving a supercritical fluid.

Increased incorporation of latex modifiers or any organic elastomer forthat matter, within a silica aerogel matrix will likely be promoted byderivitization with a reactive silane coupling agent. Such a strategyhas been used extensively by the tire industry to improve theincorporation and adhesion of silica/alumina modifiers within asynthetic rubber matrix, a process known to vastly improve themechanical durability and abrasion resistance of these materials.Sulfur-based silane coupling agents, such asbis(triethoxysilylpropyl)tetrasulfide (TESPT) ormercaptopropyl-trimethoxysilane (MPTS), are typically used in thisprocess. At elevated temperatures, the sulfur-based moieties in thesecoupling reagents are known to react with the unsaturated sites of asynthetic or natural rubber (i.e. polyisoprene), a crosslinking processknown as vulcanization (FIG. 1). This vulcanization process has beenshown to improve the overall durability and elasticity of a rubber-basedmaterial, attributes that are desirable for a material intended for usein an inflatable habitat.

A simplified schematic showing our approach is shown in FIG. 2. Theapproach basically consisted of a two-step process: (1) modification ofpoly(styrene-butadiene) latex with sulfidosilane coupling agentsfollowed by (2) co-hydrolysis and condensation with silica precursors(TEOS, polyethylsilicate, etc). The use of modified latex emulsions inthis fashion should allow for a significant increase in organic loadingswithout sacrificing mechanical or thermal performance. This is in starkcontrast to the materials prepared with unmodified polymeric emulsionswhich could only be prepared at a maximum organic content of 30 wt %.The use of more reactive polymeric modifiers was expected to affordaerogel-based insulation materials with a significant elastic modulus,sufficient radiation protection and superior thermal protection.

Vulcanization of Styrene-Butadiene Latex Aqueous Emulsions—Preparationof Silane Functionalized Polymers

Shown in Table 1 are the conditions and formulations used to preparevulcanized/modified latex particles. In general, ethanol solutions ofsulfidosilane coupling agents were added to aqueous solutions of latex,activator and metal oxide. Activators used for this vulcanizationprocess were proprietary fatty-acid zinc salts (73 LM and ZB 47)available from Struktol Corporation. The use of these soluble zinc saltshave been specifically shown to rapidly increase the cure kineticsduring sulfur vulcanization processes. The specific latex used in allformulations was UCAR DL313, a SBR (styrene-butadiene rubber) emulsionwith an average particle size of 0.1 μm available from Dow Chemical.Dilute mixtures of latex, activator and metal oxide were refluxed for aspecified period of time to affect vulcanization. The kinetics andreactivity of each vulcanization process was closely monitored by FT-IRspectroscopy and particle size analysis.

TABLE 1 Conditions and formulations used to prepare vulcanized latexmixtures. Coupling Agent Latex Activator Metal Oxide Sample Weight EtOHWeight H2O Weight Weight ID Identity % Add Identity % Add Identity %Identity % TV-1 TESPT 35 5x UCAR 65 4x 73 LM & 1 nano- 0.5 DilutionDL313 Dilution ZB 47 ZnO₂ TV-2 TESPT 35 none UCAR 65 none 73 LM 5 nano-5 DL313 ZnO₂ Me-1 MPTS 35 3x UCAR 65 3x none n/a none n/a Dilution DL313Dilution

The change in particle size distribution for latex emulsions treatedwith either MPTS or TESPT coupling agents was assessed using a LA910particle size analyzer (FIG. 3). Untreated UCAR 313 latex emulsionsexhibited a sharp distribution with 90% of the particles possessing anaverage diameter of 0.1840 μm. Treatment of this latex emulsion with adilute solution of TESPT caused the diameter of the particles toincrease slightly (0.2237 μm). Treatment with MPTS under diluteconditions afforded similar results, i.e. slight increase in averagediameter. However, treatment with TESPT at higher concentrations yieldedmuch larger particles with a significantly wider distribution. Here 50%of the particles were found to be in the diameter range 106.05 μm and90% in the 405.91 μm diameter range. The increase in particle size forall treatments was indicative of a vulcanization process in whichappreciable inter-particle crosslinking occurs. These results suggestthat this coagulation phenomenon was highly dependent on reactionconcentration and can be avoided by performing the vulcanization processunder dilute conditions.

Fourier Transform Infrared Spectroscopy

The vulcanization process of SBR latex emulsions was closely monitoredvia FT-IR spectroscopy. Shown in FIG. 4 are the FT-IR spectra of neatMPTS and the Me-1 latex emulsion before and after vulcanization. Evidentin the spectra for both MPTS and Me-1 prior to vulcanization is a weakband centered at 2560 cm⁻¹. This band is attributed to the presence ofS—H groups and is noticeably absent in the spectra for Me-1 aftervulcanization. The IR spectrum for the vulcanized latex instead,exhibited a strong C—S stretch centered at 700 cm⁻¹. The appearance ofthis peak and the lack of any peaks attributable to S—H was suggestiveof a near complete vulcanization process involving the addition ofsulfur across unsaturated sites in the latex emulsion. Coupled with theincrease in average particle size observed upon vulcanization, one mayassume that the latex particles effectively contain sufficienttrialkoxysliane species to participate in sol-gelhydrolysis/condensation reactions. The use of these emulsions will thuslikely result in the formation of a hybrid aerogel material possessingthe mechanical properties of an elastomeric rubber compound.

Shown in FIG. 5 are the spectra of neat MPST in comparison to twostyrene-butadiene latex emulsions vulcanized in the presence of MPST.The efficacy of vulcanization is clearly demonstrated by an increase inthe intensity of the S—C stretch centered at 700 cm⁻¹. Absent in thespectra is a broad peak centered at 1050 cm⁻¹, typically attributed toSi—O—Si stretching modes. Instead, well defined peaks centered at higherwavenumbers are observed (1165, 1100 and 1073 cm⁻¹) which can beattributed to the presence of Si—OEt groups. This observation suggeststhat the conditions used for vulcanization do not result in prematurehydrolysis (and condensation) of the Si—OEt species and results in alatex emulsion with a well-defined and meta-stable surface chemistry.This will thus allow for the effective use of this latex emulsion insol-gel reactions by providing a means to precisely control the kineticsand rate of hydrolysis of this precursor during aerogel preparation.

Preparation of Vulcanized Latex/Aerogel Composites

Shown in Table 2 are the identities and composition of aerogelcomposites prepared with vulcanized SBR emulsions. A range of latexloadings from 10 to 50 wt % were prepared, characterized and compared toa control sample prepared with an untreated latex emulsion. The requiredamount of latex emulsion was added to a previously hydrolyzed solutionof tetraethylorthosilicate. After stirring for a minimum of two hours,the resulting mixture was combined with a small amount of ethanolicammonium hydroxide to affect condensation and the formation of a rigid,coherent wet gel. The wet gel was aged overnight at 60° C. in a solutionof ammonium hydroxide in ethanol (1 vol %). After aging, solvents wereremoved using standard supercritical CO₂ extraction procedures to affordhighly flexible aerogel composites.

TABLE 2 Composition and identity of aerogel samples prepared withvulcanized SBR emulsions. Target Density Latex Silica Sample ID Latex(g/cc) Weight % Weight % Control Untreated 0.065 10 90 UCAR 313 10% Me-1Me-1 10 90 10% TV-1 TV-1 10 90 30% TV-2 TV-2 30 90 50% TV-2 TV-2 50 50

Thermal Conductivity and Density Evaluation

Shown in Table are the measured density and thermal conductivity valuesfor hybrid aerogels prepared using vulcanized SBR emulsions. With theexception of aerogels prepared from TV-2, the measured thermalconductivities and densities are essentially identical to the controlsample. Remarkably, aerogels composed of 50 wt % styrene-butadiene havenearly identical thermal conductivities to the control sample. It isimportant to note that this level of organic incorporation is notpossible without prior derivitization/functionalization with thesulfidosilane coupling agents. Samples with an elevated organic contentexhibited a lower final density (0.1 g/cc), which suggests that thedegree of process shrinkage and gel syneresis is considerably reducedfor these materials relative to standard silicate aerogels.Qualitatively, these samples exhibited a reduced dust load relative toall control samples.

TABLE 3 Density and thermal conductivity values of hybrid silicaaerogels prepared using vulcanized SBR emulsions. Final Density ThermalConductivity Sample ID (g/cc) (mW/mK) Control 0.123 13.1 10% Me-1 0.12412.7 10% TV-1 0.138 13.0 30% TV-2 0.123 n/a 50% TV-2 0.100 13.8

Fourier-Transform Infrared Spectroscopy

Shown in FIG. 7 are the FT-IR spectra of two hybrid aerogels doped with10 wt % TV-1 emulsion (blue) and 50 wt % TV-2 emulsion (red). Present inboth spectra are peaks centered at ˜2900 cm⁻¹ attributable to thepresence of aliphatic C—H groups, resulting from the effectiveincorporation of styrene-butadiene elastomers into the silicate network.At a nominal loading of 50% latex, the intensity of these peaksincreases significantly, suggesting that the organic content for thesematerials is significant. The spectra also exhibit a weak to moderatepeak centered at 700 cm⁻¹, which is attributable to the presence of S—Cbonds. The observation of these peaks suggests that the vulcanizationprocess has occurred and that effective coupling of the sulfidosilanesto the SBR emulsion has been obtained.

Thermal Gravimetric Analysis (TGA) and Differential Scanning Calorimetry(DSC)

Shown in FIG. 8 and FIG. 9 are the TGA and DSC curves for latex/rubberaerogel composites prepared from the vulcanizates prepared via thereaction of a styrene-butadiene emulsion (UCAR DL313) withBis-[3-(triethoxysilyl) propyl] tetrasulfide (referred here as TESPT oras TV-1 in sample ID) and mercaptopropyltriethoxysilane (Me-1 as sampleID). Also included in the analysis is a latex/aerogel composite preparedwithout prior vulcanization. Because all materials contain the samenominal organic content (10%), they exhibit nearly identical weightlosses from ambient to 500° C. However, evidence of vulcanization andincreased crosslink density for TV-1 and Me-1 samples is observed in theDSC trace from 220 to 280° C. At this temperature range, all of thecomposites exhibit a mild exothermic transition with complete weightretention. This transition is attributed to the thermally inducedcrosslinking of the SBR latex, with oxidation and decompositionoccurring at a higher temperature of 310° C. In comparison to theTEOS/latex control sample, the vulcanized materials do not exhibit asmooth and rapid exothermic transition. Instead, the transition is broadand ill-defined. This is evidence of prior crosslinking and demonstratesthe successful vulcanization and functionalization of the SBR emulsionprior to sol-gel synthesis. It is important to note that this TGA/DSCanalysis indicates that these rubber/aerogel materials are stable wellabove the maximum observed temperature at the lunar surface (˜120° C.).

Porosimetry Evaluation

Shown in FIG. 10 are the nitrogen physisorption isotherms for vulcanizedlatex/aerogel composites. As evidenced by the rapid adsorption at highpressures and the formation of a Type IV isotherm, all of the solidspossess a large population of interconnected mesopores (2-50 nm). Thisbehavior is consistent with the formation of a high-surface-area aerogelmaterial. Calculated surface areas and pore size distributions obtainedfrom the analysis of the N2 physisorption isotherms confirms thisassertion (Table 4).

TABLE 4 Surface areas, pore volume and mean pore diameter calculated forvulcanized latex/aerogel composites. Surface Area Pore Volume PoreDiameter Sample ID (m²/g) (cm³/g) (nm) TEOS 973 3.26 9.41 TEOS-L 9664.08 11.87 10% Me-1 1011 3.94 11.02 10% TV-1 876 3.66 11.84

Mechanical Property Evaluation—Compressive Recovery

It is expected that the packaging and deployment of an inflatablehabitat will subject materials to moderate compressive and tensilestresses. It is thus vitally important to assess the impacts ofmechanical stress on the overall material properties of the hybridaerogel composites developed during this program. The results ofrepeated flexure and repeated compressive events on materialthermophysical properties of prototype aerogel material are describedbelow. Additionally, the stress-strain curves of some prototypecomposites and determined compressive moduli are also described below.

Compressive Strength Evaluation

The compressive properties of hybrid aerogels prepared with variousamounts of emulsified elastomer were determined using an Instron model5569, a 50 kN load cell and a crosshead speed of 0.06 in/min. TheYoung's moduli for candidate aerogels were determined by calculating theslope in the elastic region of the stress-strain curve. Shown in Table 5are the calculated compressive moduli and the observed change in thermalperformance upon compression for hybrid aerogels containing variousamounts of vulcanized and untreated UCAR 313 latex. A slight change incompressive strength was observed for materials prepared with vulcanizedlatex emulsions, presumably due to an increase in crosslink density thatoccurs upon vulcanization for the styrene-butadiene elastomer (FIG. 12).While the effect is subtle, it is expected that an optimization of thevulcanization process should afford aerogels with an improvedcompressive strength.

TABLE 5 Young's modulus and effects of compression on the thermalperformance of hybrid aerogel formulations. Thermal Thermal Conduc-Final Conduc- Young's tivity After Density tivity Modulus CompressionSample ID Latex (g/cc) (mW/mK) (PSI) (mW/mK) Control Untreated 0.12313.1 30 14.1 UCAR 313 10% Me-1 Me-1 0.124 12.7 36 15.9 10% TV-1 TV-10.138 13.0 42 14.2

Assessment of Compressive Elasticity (Recovery)

The compressive elasticity of hybrid aerogels prepared with variousamounts of emulsified elastomer was determined using an Instron model5569, a 50 kN load cell and a crosshead speed of 0.01 in/min. Afterpreloading to a pressure of 0.004 PSI, 2 in×2 in samples were compressedto a total load of 14 PSI. The compressive recovery was assessed bydetermining the change in thickness immediately after and 5 minutesafter the compressive load. The latter point was acquired afterobserving that many samples do not exhibit an immediate recovery. Thecompressive recovery for a number of hybrid aerogel samples preparedwith vulcanized styrene-butadiene emulsions are shown in Figure. Asevidenced by the data, increases in organic content unfortunately have adetrimental effect on compressive elasticity. Specifically, aerogelscontaining a nominal organic content of 50% exhibited a 5 min recoveryof 78% versus 97% for a pure silica control sample.

Despite the fact that the inferior compressive elasticity observed forthe high organic content materials are presumably resulting from thecollapse of a finite population of macropores, it is still likely thatthe silicate backbone is sufficiently robust to retain microporosity.Impacts to thickness and density are however, expected to be fairlymoderate. Shown in FIG. 14 are the changes in thermal conductivity anddensity for hybrid aerogel composites after three successive compressiveloads to 14.7 PSI. It is important to note that a large number of thehybrid aerogels exhibit changes in thermal conductivity equal to orbetter than that observed for the silica-based control sample.Consistent with the previously described inferior compressive recoveryresults, samples with an appreciable amount of organic content exhibit adensification of nearly 50%.

Functionalizing in Non-Polar Solvents and Preparing Gel Composition

Functionalizing unsaturated organic polymers such as polyolefins withsulfidosilanes is highly attractive in that it can be conducted inaqueous systems using suitable latex emulsions. In one embodiment,sulfur-functionalization of the unsaturated organic polymers areperformed in aqueous medium. Alternatively, they may be conducted onnon-aqueous medium. In some instances, aqueous vulcanization processesmay be sluggish, leading to material heterogeneity via coagulation andcan initiate premature hydrolysis of alkoxysilane moieties. In anotherembodiment, the present invention employs a non-aqueous vulcanizationprocess to affect derivitization of polybutadiene.

The vulcanization process is used to transform natural or syntheticpolyolefin into a thermoset resin with the main goal of improvingdurability, thermostability, elasticity and tensile strength (FIG. 15).Activator loading, reaction concentration, reaction time and reactiontemperature are important for vulcanization process. As such, theeffects of, (1) activator concentration, (2) reactant concentration and(3) sulfidosilane coupling agent concentration on the molecular weightand reactivity of the vulcanizate formed from the reaction ofpolybutadiene w/TESPT may be used to alter or engineer the reactivityand molecular weight of the vulcanizate that affect the final propertiesof the resulting aerogel composite.

The derivitization/vulcanization process used in an embodiment involvesthe reaction of polybutadiene and TESPT coupling agent (structure shownin FIG. 16) in refluxing non-polar solvents (toluene, dioxane, etc.) fora period of 6 hours. Reactant concentrations, coupling agentconcentrations and activator contents were varied according to the dataprovided in Table. The specific activator used was 73-LM, a proprietarymixture of fatty acid zinc salts produced by Struktol Corporation tospecifically promote low temperature vulcanization processes. Afterrefluxing, the product mixtures were characterized via infraredspectroscopy and gel permeation chromatography to assess reactivity andpolymer molecular weight.

FIG. 17 illustrates the Fourier Transform infrared (FT-IR) spectrum ofWD-32 vulcanizate in comparison to pure polybutadiene. Absent in thespectra is a broad peak centered at 1050 cm⁻¹, typically attributed toSi—O—Si stretching modes. Instead, well defined peaks centered at higherwave numbers are observed (1165, 1100 and 1073 cm⁻¹) which can beattributed to the presence of Si—OEt groups. This observation suggeststhat the conditions used for vulcanization do not result in prematurehydrolysis (and condensation) of the Si—OEt species, allowing for thepossible use of the vulcanizate in standard acid-base sol-gel reactions.Present in the spectra for polybutadiene is a weak band centered at 1637cm⁻¹. This peak is attributable to the presence of olefinic (C═C)species. The decrease in the relative intensity (˜50%) of this peak uponvulcanization is evidence of carbon-sulfur bond formation and theformation of a crosslinked polymer possessing reactive trialkoxysilanemoieties. The appearance of a peak at ˜700 cm⁻¹ is evidence ofcarbon-to-sulfur (monosulfide and/or disulfide) bond formation.

All of the vulcanizates prepared in Table 6 were characterized via gelpermeation chromatography (GPC). This analysis is particularly powerfulin that it will not only allow one to assess changes in the molecularweight of the vulcanizate, it can be used to approximate product yieldby monitoring the disappearance of peaks attributable to TESPT(retention time=11.2 min, M_(w)=600). Shown in FIG. 18 are a series ofGPC chromatograms for polybutadiene/TESPT vulcanizates in comparison topure polybutadiene. Evident in these vulcanizates are low molecularweight species (TESPT), the presence of which indicates a product yieldof less than 100%. Given that the nominal loading of TESPT is knownprior to each vulcanization reaction, it is possible to calculate theproduct yield based on the change in relative peak areas for TESPT andPBD obtained from GPC analysis. Shown in Figure are the peak molecularweights and product yields as determined by GPC analysis for a number ofvulcanization reactions performed. The molecular weight of thevulcanizate of the invention is directly proportional to both couplingagent concentration and activator content. Clearly, increases in bothresult in an appreciable increase in crosslink density and a highermolecular weight vulcanizate. This increase in crosslink density willlikely have an appreciable effect on the elasticity, durability andmechanical properties of a hybrid aerogel prepared with these particularvulcanizates. Product yields for this vulcanization process seem to bemostly favored by low activator content and high coupling agentconcentrations.

Preparation of Hybrid Gels

This process is a co-condensation of vulcanized Polyburadiene(PBD)-Si(OEt)₃ and silica from TEOS. As vulcanized PBD-Si(OEt)₃ cannotbe dissolve in ethanol, dioxane was chosen as the solvent in thecondensation reaction, which is a non-alcoholic sol-gel process.Additionally, a fiber reinforcement may be added to the gels to producea wet gel sheet that may be subsequently dried to produce aerogelcomposites. Polyester fiber reinforced aerogel composites were preparedat various vulcanizate loadings ranging from 0 to 50 wt %. All materialswere prepared at a low target density of 0.05 g/cc in order to maximizethermal performance when measured at low pressures (i.e. vacuum). Agingwas done at RT, overnight and afterwards 1% NH3-6.25% HMDZ in EtOH, at55° C. for ˜30 hrs.

As can be seen from FIG. 20 that even for target density of 0.07 g/ccand final density of ˜0.10 g/cc, the aerogel coupons are very flexibleeven with 17 wt % Polybutadiene-PBD-PESPT doping. For the same targetdensity, the aerogel coupons without PBD-PESPT doping are very rigid andcould not bend without aerogel particle shattering.

The relatively short gel times of WD-35F (30 minutes) are remarkablegiven that these materials contain 50% organic polymer. This level ofreactivity clearly indicates that the vulcanization process affords afunctionalized polymer that is highly reactive in hydrolysis andcondensation reactions. It is also worthwhile to note that these shortgel times improve the compatibility of these materials with economicallyfeasible large scale manufacturing processes. A cursory analysis of theas-prepared aerogel composites indicate that flexibility, durability andelasticity of these materials are directly related to the organiccontent of the composite. The incorporation of a vulcanized rubbercomponent to these aerogel composites is clearly imparting a positiveeffect on the mechanical properties of these materials.

Thermal Conductivity and Density Evaluation

Shown in Figure-FIG. 22 are the measured ambient thermal conductivityand density values for rubber/silica aerogel composites prepared withvarious PBD vulcanizates. The thermal conductivity values for all thefinal materials are directly proportional to their respective organiccontent. Without limiting to one particular theory, applicants postulatethat the substantial incorporation of polymeric materials likely resultsin the formation of macropores and a subsequent increase in convectiveheat transfer. respectively. The data shown in Figure indicate thatfinal densities as low as 0.065 g/cc were achievable with this currentapproach.

Infrared Spectroscopy

Shown in Figure is a FT-IR spectra of an aerogel composite prepared witha low molecular weight PBD vulcanizate (WD-23). This material has anominal organic content of 50 wt %, and displays obvious peaksattributable to the presence of olefinic and methylene groups. While theintensity of these peaks is clearly dominated by the presence of anintense Si—O—Si asymmetric peak at 1060 cm⁻¹, these results are clearlysuggestive of substantial incorporation of organic content. The FT-IRspectra of other hybrid silica/PBD aerogel composites are essentiallyidentical and clearly show evidence of high levels of organic content.

Surface Area and Porosity Evaluation

BET surface area of hybrid decreases with increasing PBD content. Asshown in FIG. 24 and Table 6, hybrid with 0, 17, 33% PBD are 950-930m2/g and surface area decreased dramatically to 630 m²/g with 50% PB.This might be the reason for increased TC with increasing PBD content inhybrid aerogel.

TABLE 7 Scaled up experiments WD-35c, d, e, f (same as WD- 31) using G80fiber. Coupon size: 8″ × 8″. Total H2O/SiO2 molar ratio for TEOS orPBD-PESPT was 4. Sample ID WD-35C WD-35D WD-35E WD-35F PBD-PESPT wt % in0 17 33 50 total solid Final density (g/cc) 0.12 0.11 0.09 0.09 TC(mW/m-K) 11.6 13.3 15.5 18.2 BET surface area (m2/g) 946.3 945.9 932.9631.0 Average desorption 2.84 3.20 2.92 1.90 pore volume (cm2/g) Averagedesorption 8.36 10.56 10.62 10.40 pore diameter (nm)

Recovery After Compression

The compressive recovery was determined using an Instron model 5569, a50 kN load cell and a crosshead speed of 0.05 in/min After preloading toa pressure of 0 psi, 2 in×2 in samples were compressed to a total loadof 14.7 psi and then the stress was released to 0 psi. The strain at 0psi is the final strain of the sample after compression. As shown inFIG. 25, the strain at 0 psi for 33% PBD-PESPT is 1%, which means thatthe recovery of the sample thickness is 99%. All hybrid aerogels showedrecovery above 97%.

Hydrophobicity Evaluation

While atmospheric degradation of these materials is not expected to be aconcern in a lunar environment, they will be subject to various levelsof humidity prior to launch and deployment. The hydrophobicity of allrubber/aerogel composites have thus been assessed via water contactangle measurement. Surprisingly, materials with nominal organic loadingsapproaching 50 wt % exhibit very high water contact angles regardless ofaging conditions (hexamethyldisilazane vs. ammonium hydroxide). Thislevel of inherent hydrophobicity is indicative of significant polymerincorporation and is consistent with our infrared spectroscopicevaluation. These results are significant because it suggests that ourstandard wet-gel aging conditions can be significantly shortened ormodified by eliminating the use of a standard hydrophobe agent,hexamethyldisilazane.

Consistent with the previously described inferior compressive recoveryresults, samples with an appreciable amount of organic content exhibit adensification of nearly 50%. The final materials may be further enhancedby improving the homogeneity of polymer incorporation, reducing themacroporosity of the composites and improving the overall compressiveelasticity of high organic content aerogel materials.

Thermal Performance Testing Under Vacuum Test Method Description

In order to measure the thermal conductivity of low density materialssuch as the hybrid aerogels of the present invention, a guarded hotplate apparatus based on a slightly modified ASTM C177-85 design wasused. This unit is capable of obtaining thermal conductivity values inthe temperature range of −200° F. to 600° F. Examples of materials thathave been tested in this apparatus are insulating foams, graphite foamsand fibrous insulations, low density ceramic insulations, cloths andrubbers.

This apparatus is capable of operating in a vacuum down to 10⁻⁵ torr(10⁻⁶ torr if the material is clean). The apparatus consists of acentral heater plate surrounded by a guard heater, each separatelycontrolled. The guard ring is maintained at the same temperature as thecentral heater so that all of the heat flow is normal to the specimensurface. The temperature differences between the guard and the centralsections are measured by means of differential thermocouple junctionsconnected in series. The heater plate is sandwiched between layers ofinterfacial material, the hot face thermocouples, the specimen, coldface thermocouples, interfacial material, and finally a cold source todissipate the heat. In addition to the thermocouples in contact with thespecimen, thermocouples are located in the central heater and outercopper cold plates. FIG. 27 shows a schematic of a typical hot plateapparatus.

To provide intimate contact at all interfaces, the entire sandwichassembly is pressed firmly together by spring loading with the totalload application desired, which is usually 600 pounds. For fragilespecimens spacers are used to maintain specimen thickness. Spacersmaintain a fixed distance between the heater and the cold plate. Forspecimens greater than 0.250 in thick internal thermocouples are used.These thermocouples consist of 0.005 in diameter wire in a 0.040 indouble bore alumina tube. To obtain mean sample temperatures above roomtemperature, water is circulated through the cooling section.Equilibrium conditions are obtained before readings are taken.

Thermal conductivity values were calculated from the followingexpression:

k_(s)=Q l_(s)/AΔt

where

-   -   Q=total heat flow (Btu/hr)    -   l_(s)=average thickness of specimen (inches)    -   A=area of central heater section (ft²)    -   Δt=sum of temperature drop across sample (° F.).

Theoretically, Q, the heat input, should split, with exactly half of theinput flowing through each sample. The temperature drops indicate thatthis condition rarely exists. Instead, there is a slight unbalance inheat flow. The above formula then permits a calculation of thearithmetic average for the two panels. In this calculation thetemperatures are measured directly at the faces of the specimen by thegetters, resulting in a direct method.

Thermal Performance Results & Discussion

A low density hybrid rubber/aerogel composite containing a nominalorganic loading of 17 wt % (WD-35D) was subjected to thermalconductivity testing according to the methods discussed above.Specifically, the thermal conductivity at 100° F. was determined at anambient pressure and under high vacuum (3.5×10⁻⁴ Torr). All samples weretested at a compressive load of 0.4 PSI, a thickness of 0.25 in and afinal density of 0.0764 g/cc. Interestingly, the values observed forthese hybrid aerogel composites compare very favorably to those observedfor multi-layer insulation. It is particularly well known that MLI-basedinsulation systems are highly sensitive to compressive events and willthus exhibit variable thermal conductivity values ranging from 1.1 and5.5 mW/m·K when tested under the same conditions. In contrast, theaerogel-based materials of the present invention are largely insensitiveto the compression events associated with the rigors of packing anddeployment.

The thermal conductivity of any material under high vacuum results fromthe combination of radiative and solid conductivity heat transfer. Thehybrid aerogels of the present invention were specifically prepared atlow densities to minimize the contributions of heat transfer from solidconductivity. The inhibition of radiative heat transfer in thesematerials is however likely to be minimal due to the transparency ofSiO₂ to infrared radiation. At the test temperature of 100° F., it isestimated that a large portion of the thermal conductivity results fromradiative heat transfer. Further incorporation of infrared opacificationagents (i.e. carbon black) vastly improve the thermal performance ofthese materials.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1. Schematic depicting the use of coupling agents to improve theadhesion of rubber to silica

FIG. 2. Schematic depicting the modification of poly(styrene-butadiene)latex with TESPT.

FIG. 3. Particle size distribution of treated and untreated UCAR 313latex emulsions.

FIG. 4. FT-IR spectra of neat MPTS and a Me-1 latex emulsion before andafter vulcanization.

FIG. 5. FT-IR spectra of MEPST, vulcanized TV-1 latex and vulcanizedTV-2 latex.

FIG. 6. Photographs of hybrid silica/SB rubber aerogels prepared with50% TV-2 (left) and 30% TV-2 (right) latex emulsions.

FIG. 7. FT-IR spectra of silica/SBR hybrid aerogels prepared usingvulcanized latex TV-1 and TV-2.

FIG. 8. DSC curves in air of latex/aerogel composites prepared at a 10%loading.

FIG. 9. TGA curves in air for latex/aerogel composites prepared at a 10%loading.

FIG. 10. Nitrogen physisorption isotherms for vulcanized latex/aerogelcomposites.

FIG. 11. Pore size distributions for vulcanized latex/aerogelcomposites.

FIG. 12. Compressive stress strain curve of prototype aerogel compositesprepared at a nominal target density of 0.05 g/cc.

FIG. 13. Compressive recovery for hybrid aerogel composites preparedfrom the vulcanized SBR emulsions.

FIG. 14. Change in thermal conductivity and density for hybrid aerogelcomposites prepared with vulcanized SBR emulsions.

FIG. 15. Schematic depicting the vulcanization process.

FIG. 16. Molecular structure of polybutadiene and TESPT. Chain length ofPBD is longer than that shown in this figure.

FIG. 17. FT-IR spectrum of WD-32 vulcanizate in comparison to purepolybutadiene.

FIG. 18. GPC chromatograms of vulcanized polybutadiene prepared at aconcentration of 0.65 g/cc and an olefin/TESPT molar ratio of 12.5 (a)in comparison to pure polybutadiene (b).

FIG. 19. Molecular weights and product yields determined for thevulcanization of PBD with TESPT according to GPC analysis.

FIG. 20. Photographs of a fiber-reinforced hybrid rubber/silica aerogelsexemplifying the highly flexible and resilient nature of this material.

FIG. 21. Thermal conductivity values (1 atm, 100° F.) as a function oforganic content for hybrid silica/PBD aerogels prepared with a varietyof PBD vulcanizates.

FIG. 22. Measured density values as a function of organic content forhybrid silica/PBD aerogels prepared with various PBD vulcanizates.

FIG. 23. FT-IR of a rubber/silica aerogel prepared with a low molecularweight vulcanizate (WD23).

FIG. 24. Nitrogen isotherms (top panel) and pore size distribution ofPBD-silica hybrid aerogels (bottom panel). PBD content in WD-35C1, D1,E1, and F1 are 0, 17, 33 and 50 wt %.

FIG. 25. Compressive stress-strain curve for Silica-BD/PESPT aerogelwith 33% PBD-PESPT.

FIG. 26. Photograph displaying the inherent hydrophobicity of WD-23d.

FIG. 27. Schematic depicting a typical ASTM C177 guarded hot plateapparatus.

FIG. 28. Thermal conductivity (ASTM C177) of a hybrid aerogel compositeas a function of atmospheric pressure at 38° C. (100° F.).

1. A dry gel composite comprising an organic polymer and a silicanetwork, wherein the organic polymer is covalently bound to the silicanetwork through a sulfur-containing cross linking agent; and wherein thedry gel composite has a thermal conductivity at 37.5° C. and ambientpressure between 12 to 24 mW/mK.
 2. The dry gel composite of claim 1wherein the dry gel composite is an aerogel composite.
 3. The dry gelcomposite of claim 1 or claim 2, wherein the polymer is selected fromthe group consisting of unsaturated polyesters; prepolymers based onvinylesters, acrylates, methacrylates or polyurethanes, polybutadiene,polystyrene, or polyisoprene; styrene-butadiene copolymer;butadiene-isoprene co-polymer; buradiene-isoprene-styrene terpolymer;copolymer or terpolymer of isobutylene, para-methylstyrene andbromo-para-methyl-styrene; ethylene propylene diene monomer rubber and acombination thereof.
 4. The dry gel composite of claim 1 or claim 2,wherein the polymer is in the form of latex particles or polymer resins.5. The dry gel composite of claim 1 or claim 2, wherein thesulfur-containing cross linking agent is a hexasulfide compound, atetrasulfide compound, or a disulfide compound.
 6. The dry gel compositeof claim 1 or claim 2, wherein the sulfur-containing cross linking agentis selected from the group consisting of polysulfide alkyl silanes,mercapto aryl silanes, polysulfide aryl silanes, silated corepolysulfides, sulfur-containing silanes, sulfanylsilanes,sulfur-containing siloxanes, sulfur-functional polyorganosiloxanes,bis(triethoxysilylpropyl) tetrasulfide,3-thiocyanatopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane andany combination thereof.
 7. The dry gel composite of claim 1 or claim 2,wherein the sulfur-containing cross linking agent is a sulfidosilane ofa general formula (R₁—O)₃—Si—R₂—S_(x)—R₂—Si—(R₁—O)₃ or of a generalformula HS—R₁—Si—(O—R₂) where R₁ and R₂ are same or different alkyl oraryl groups; x is a number between 1 and 8
 8. The dry gel composite ofclaim 1 or claim 2, wherein the polymer in the dry gel composite ispresent up to 50 wt %
 9. The dry gel composite of claim 1 or claim 2,wherein the sulfur-containing cross linking agent in the dry gelcomposite is present up to 50 wt %
 10. The dry gel composite of claim 1or claim 2, wherein the polymer in the dry gel composite is at least 3wt %
 11. The dry gel composite of claim 1 or claim 2, further comprisingfibers up to 75 wt %.